CN101955563B - Emulsion for low-surface energy coating and preparation method - Google Patents
Emulsion for low-surface energy coating and preparation method Download PDFInfo
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- CN101955563B CN101955563B CN 200910016789 CN200910016789A CN101955563B CN 101955563 B CN101955563 B CN 101955563B CN 200910016789 CN200910016789 CN 200910016789 CN 200910016789 A CN200910016789 A CN 200910016789A CN 101955563 B CN101955563 B CN 101955563B
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- emulsion
- surface energy
- acrylate
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- methacrylate
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- 238000000576 coating method Methods 0.000 title claims abstract description 34
- 239000000839 emulsion Substances 0.000 title claims abstract description 33
- 239000011248 coating agent Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 alkyl methacrylate Chemical compound 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 22
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 230000003750 conditioning effect Effects 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 24
- 239000000872 buffer Substances 0.000 claims description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 14
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 2
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 2
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims 1
- 125000001153 fluoro group Chemical class F* 0.000 claims 1
- 229940065472 octyl acrylate Drugs 0.000 claims 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 abstract description 6
- 239000011737 fluorine Substances 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 5
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract description 3
- 238000005201 scrubbing Methods 0.000 abstract description 3
- 230000002688 persistence Effects 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 2
- 239000006172 buffering agent Substances 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 230000005923 long-lasting effect Effects 0.000 abstract 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002221 fluorine Chemical class 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000006072 paste Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 201000004681 Psoriasis Diseases 0.000 description 1
- 206010038743 Restlessness Diseases 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses emulsion for a low-surface energy coating and a preparation method. The emulsion is characterized in that: the emulsion is prepared by copolymerizing fluorine-containing acrylate, fluorine-silicon macormonomers, alkyl methacrylate, alkyl acrylate and hydroxyalkyl acrylamide under the action of water, an emulsifier, an initiator, a PH value buffering agent and a PH value conditioning agent. The preparation method is characterized by comprising the following steps of: adding the water, the initiator, the emulsifier and the PH value buffering agent into a reaction kettle according to proportion; adding dropwise the mixed solution of the alkyl methacrylate, the alkyl acrylate, the hydroxyalkyl acrylamide, the fluorine-containing acrylate and the fluorine-silicon macormonomers into the reaction kettle for reaction according to proportion; and finally adding the PH value conditioning agent into the reaction kettle to condition a PH value to prepare the emulsion for the low-surface energy coating. The emulsion for the low-surface energy coating prepared by the preparation method has the characteristics of stable reaction process, relatively higher product stability, high scrubbing resistance, high saltwater resistance, high salt fog resistance, high acid and alkali resistance, high ageing resistance, high paste-resistant persistence and the like. The coating produced by using the emulsion for the low-surface energy coating has relatively lower surface energy and long-lasting effect, forms the contact angle of more than 100 degrees with the water and forms the contact angle of more than 70 degrees with diiodomethane.
Description
Technical field:
The present invention relates to coating with emulsion and production technical field, be specially a kind of emulsion for low-surface energy coating and preparation method.
Background technology:
Low surface energy coatings has hydrophobic, oleophobic property is widely used in the protection of the materials such as Architectural Equipment, bridge, boats and ships, offshore platform, terminal facilities, electronic product, engineering machinery, historical relic's protection, leather, woodenware and prevents that the unrest of communal facility from the field such as pasting, scrawling.Especially in recent years " city psoriasis " phenomenon is day by day serious, develops the water-based anti-sticking dope of a kind of difficult adhesion glue, paste and pressure sensitive adhesive, is used for appearance protection and the decoration of urban architecture engineering, is conducive to the modern city civilization construction.Because low surface energy coatings has hydrophobic, oleophobic property, glue, paste, pressure sensitive adhesive etc. are very poor to its sticking power of filming, and the small advertisement of pasting on it has certain " certainly sticking up property ", Exposure to Sunlight, wind, drench with rain or the effect of other external force under can come off easily; Ink, the oil pen, the coating that self-spraying paint is filmed to low surface energy coatings is also very poor, self-spraying paint is sprayed on above it and is " two-layer skin " state, be easy to remove, so a lot of departments are all at the research and development low surface energy coatings, but owing to lack this water-soluble low surface energy paint emulsion on the Vehicles Collected from Market, therefore, many researchs are to rely on to add low surface energy auxiliary agent (wax class, the silicon class, fluorine class etc.) realize the low surface energy anti-adhesion effects with coating main film forming substance (being emulsion) by physical blending, this class low surface energy coatings since the low surface energy auxiliary agent that adds and filmogen can not be combined or in conjunction with insufficient with chemical bonded refractory, therefore a series of shortcomings of this class coating have been caused, easily dirty such as some " bellding ", some anti-adhesion effects is poor, after pasting repeatedly, some can lose non-stick property, some short-term is exposed to the sun and rain and is just lost non-stick property etc., some domestic and imported product expensive etc.
Summary of the invention:
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art, provide can ambient self-crosslinking a kind of emulsion for low-surface energy coating and preparation method.
The present invention can reach by following measure:
A kind of emulsion for low-surface energy coating, it is characterized in that by fluorinated monomer, the large monomer of fluorine silicon, alkyl methacrylate, alkyl acrylate, the hydroxyalkyl acrylamide is at water, emulsifying agent, initiator, copolymerization forms under the effect of pH value buffer reagent, and the mass percent of each composition is: fluorinated acrylate 1～30%, the large monomer 1～20% of fluorine silicon, alkyl methacrylate 10～40%, alkyl acrylate 5～35%, hydroxyalkyl acrylamide 0.5～5%, water 40～50%, initiator 0.05～1%, emulsifying agent 0.1～4%, pH value buffer reagent 0.1～1%.
The present invention can add an amount of PH conditioning agent, to regulate the pH value of emulsion.
The general formula of the large monomer of fluorine silicon of the present invention is:
R1 wherein, R2, R4 are any one in methyl, ethyl, propyl group, butyl, isobutyl-, the phenyl etc.; The general formula of R3 is CF3 (CF2) m (CH2) n-or H (CF2) x (CH2) n-, wherein m 〉=0, n=2～8, x 〉=2; A=2 in the large monomer of fluorine silicon～8, b 〉=3, c 〉=3.
Fluorinated acrylate of the present invention is a kind of or any several mixture in trifluoroethyl methacrylate, vinylformic acid trifluoro ethyl ester, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, vinylformic acid octafluoro pentyl ester, methacrylic acid octafluoro pentyl ester, vinylformic acid 19 fluorine esters, the vinylformic acid perfluoro capryl ethyl ester etc.
Alkyl methacrylate of the present invention is a kind of or several arbitrarily in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid (different) monooctyl ester, 2-Ethylhexyl Methacrylate, lauryl methacrylate(LMA), stearyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester, the methacrylic acid hydroxy butyl ester etc.
Alkyl acrylate of the present invention is a kind of or several arbitrarily in methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, vinylformic acid (different) monooctyl ester, 2-EHA, lauryl acrylate, octadecyl acrylate, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, the vinylformic acid hydroxy butyl ester etc.
PH value buffer reagent of the present invention is any one in yellow soda ash, sodium bicarbonate, sodium phosphate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, bicarbonate of ammonia, the ammoniacal liquor etc.
Emulsifying agent of the present invention is non-reactive emulsifier, contains any several composition in the reactive emulsifier of unsaturated double-bond.
Initiator of the present invention is a kind of in Potassium Persulphate, the ammonium persulphate.
The present invention is with fluorinated acrylate, the large monomer of fluorine silicon, alkyl methacrylate, alkyl acrylate, the monomers such as hydroxyalkyl acrylamide are at water, emulsifying agent, initiator, the effect of pH value buffer reagent is carried out letex polymerization and is formed, make fluorine, silicon is combined on the acrylate side chain with the chemical bond form, utilize organic fluorine, the excellent performance of silicon realizes modification to acrylate resin, obtained a kind of emulsion for low-surface energy coating, it films hydrophobic strong with the oleophobic ability, the surface energy of filming is lower, effect is lasting, with the contact angle of water greater than 100 °, with the contact angle of methylene iodide greater than 70 °.
A kind of preparation method of emulsion for low-surface energy coating is characterized in that step is:
The 1st step joined water, initiator, emulsifying agent, pH value buffer reagent in the reactor in proportion, was warming up to 60～80 ℃,
Second step, the mixed solution to reactor dropping alkyl methacrylate, alkyl acrylate, hydroxyalkyl acrylamide, fluorinated acrylate, the large monomer of fluorine silicon reacts in proportion, lower the temperature behind reaction times 4～12h,
The 3rd step, survey pH value, pH value is 7.0～9.0 get final product, can add an amount of pH value conditioning agent in reactor, with the accent pH value.
The emulsion for low-surface energy coating reaction process that the present invention produces is stable, and product stability is better, and the surface energy of filming is lower, effect lasting, excellent scrubbing resistance is arranged, salt water resistance salt fog, acid and alkali-resistance, the performance such as ageing-resistant
Description of drawings:
Fig. 1 is the synoptic diagram of 106.2 ° of the contact angles of water.
Fig. 2 is the synoptic diagram of 115.4 ° of the contact angles of water.
Fig. 3 is 75.1 ° of synoptic diagram of contact angle of methylene iodide.
Fig. 4 is 83.5 ° of synoptic diagram of contact angle of methylene iodide.
Embodiment:
The invention will be further described below in conjunction with embodiment,
Embodiment 1:
The mass percent of composition and composition:
1. the large monomer 6.0g of fluorine silicon
2. fluorinated acrylate 5.5g
3. alkyl methacrylate 17.1g
4. alkyl acrylate 15.0g
5. hydroxyalkyl acrylamide 3.5g
6. emulsifying agent 4.3g
7.PH value buffer reagent 0.2g
8. initiator 0.4g
9. water 48.0
10.PH the value conditioning agent is an amount of
Preparation process is:
The 1st step joined water, initiator, emulsifying agent, pH value buffer reagent in the reactor, was warming up to 60 ℃,
Second step, the mixed solution that reactor adds alkyl methacrylate, alkyl acrylate, hydroxyalkyl acrylamide, fluorinated acrylate, the large monomer of fluorine silicon reacts, lowers the temperature behind the reaction times 4h,
The 3rd step, survey pH value, pH value is 7.0 get final product, can add an amount of pH value conditioning agent in reactor, with the accent pH value.
Embodiment 2:
The mass percent of composition and composition:
1. the large monomer 6.5g of fluorine silicon
2. fluorinated acrylate 9.0g
3. alkyl methacrylate 17.8g
4. alkyl acrylate 15.1g
5. hydroxyalkyl acrylamide 1.8g
8. emulsifying agent 4.2g
10.PH value buffer reagent 0.3g
11. initiator 0.4g
12. water 48.0
10.PH the value conditioning agent is an amount of
Preparation process is:
The 1st step joined water, initiator, emulsifying agent, pH value buffer reagent in the reactor, was warming up to 80 ℃,
Second step, the mixed solution that reactor adds alkyl methacrylate, alkyl acrylate, hydroxyalkyl acrylamide, fluorinated acrylate, the large monomer of fluorine silicon reacts, lowers the temperature behind the reaction times 4h,
The 3rd step, survey pH value, pH value is 7.0 get final product, can add an amount of pH value conditioning agent in reactor, with the accent pH value.
Embodiment 3:
The mass percent of composition and composition:
1. the large monomer 8.0g of fluorine silicon
2. fluorinated acrylate 7.0g
3. alkyl methacrylate 16.1g
4. alkyl acrylate 13.5g
5. hydroxyalkyl acrylamide 2.8g
6. emulsifying agent 3.8g
7.PH value buffer reagent 0.3g
8. initiator 0.5g
9. water 48.0
10.PH the value conditioning agent is an amount of
Preparation process is:
The 1st step joined water, initiator, emulsifying agent, pH value buffer reagent in the reactor, was warming up to 70 ℃,
Second step, the mixed solution that reactor adds alkyl methacrylate, alkyl acrylate, hydroxyalkyl acrylamide, fluorinated acrylate, the large monomer of fluorine silicon reacts, lowers the temperature behind the reaction times 10h,
The 3rd step, survey pH value, pH value is 8.0 get final product, can add an amount of pH value conditioning agent in reactor, with the accent pH value.
Embodiment 4:
The mass percent of composition and composition:
1. the large monomer 8.8g of fluorine silicon
2. fluorinated acrylate 10.0g
3. alkyl methacrylate 16.6g
4. alkyl acrylate 11.4g
5. hydroxyalkyl acrylamide 1.0g
6. emulsifying agent 3.5g
7.PH value buffer reagent 0.3g
8. initiator 0.4g
9. water 48.0
10.PH the value conditioning agent is an amount of
Preparation process is:
The 1st step joined water, initiator, emulsifying agent, pH value buffer reagent in the reactor, was warming up to 80 ℃,
Second step, the mixed solution that reactor adds alkyl methacrylate, alkyl acrylate, hydroxyalkyl acrylamide, fluorinated acrylate, the large monomer of fluorine silicon reacts, and is cooled to room temperature behind the reaction times 12h,
The 3rd step, survey pH value, pH value is 9.0 get final product, can add an amount of pH value conditioning agent in reactor, with the accent pH value.
Above-described embodiment emulsion property is as follows:
| Order | Project | Index |
| Number | ||
| 1 | Outward appearance | Milky white band blue light liquid |
| 2 | Solids content % | 50±2 |
| 3 | Viscosity (25 ± 2 ℃) mpa.s | 500～3000 |
| 4 | Second-order transition temperature ℃ | 20～30 |
| 5 | Median size nm | 80～200 |
| 6 | Freeze-thaw stability (3 circulations) | Without unusual |
| 7 | PH value | 7～9 |
| 8 | Mechanical stability | Not breakdown of emulsion, without obvious throw out |
| 9 | Calcium ion stability: 0.5%CaCl 2 | 48h is without layering, without precipitation, without flocculation |
With the emulsion dilute with water in above-described embodiment, add room temperature film-forming behind an amount of film coalescence aid, test performance is as follows after the maintenance:
The present invention is combined in organic fluorine and organosilicon on the acrylate side chain with the chemical bond form, utilize the excellent performance of fluorine, silicon that acrylate is carried out modification, obtained a kind of hydrophobic and strong emulsion for low-surface energy coating of oleophobic ability, the emulsion for low-surface energy coating reaction process that the present invention produces is stable, product stability is better, and the performances such as excellent scrubbing resistance, salt water resistance salt fog, acid and alkali-resistance, ageing-resistant, anti-stick subsides persistence are arranged.The surface energy that the emulsion for low-surface energy coating that the present invention produces is filmed is lower, effect is lasting, with the contact angle of water greater than 100 °, with the contact angle of methylene iodide greater than 70 °.
Claims (9)
1. emulsion for low-surface energy coating, it is characterized in that by fluorinated monomer, the large monomer of fluorine silicon, alkyl methacrylate, alkyl acrylate, the hydroxyalkyl acrylamide is at water, emulsifying agent, initiator, copolymerization forms under the effect of pH value buffer reagent, the mass percent of each composition is: fluorinated monomer 1～30%, the large monomer 1～20% of fluorine silicon, alkyl methacrylate 10～40%, alkyl acrylate 5～35%, hydroxyalkyl acrylamide 0.5～5%, water 40～50%, initiator 0.05～1%, emulsifying agent 0.1～4%, pH value buffer reagent 0.1～1%, the general formula of the large monomer of described fluorine silicon is:
R1 wherein, R2, R4 are any one in methyl, ethyl, propyl group, butyl, isobutyl-, the phenyl; The general formula of R3 be CF3 (CF2) m (CH2) n-or H (CF2) x (CH2) n-, wherein m 〉=0, n=2～8, x 〉=2; A=2 in the large monomer of fluorine silicon～8, b 〉=3, c 〉=3.
2. a kind of emulsion for low-surface energy coating according to claim 1 is characterized in that fluorinated monomer is a kind of or any several mixture in trifluoroethyl methacrylate, vinylformic acid trifluoro ethyl ester, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, vinylformic acid octafluoro pentyl ester, methacrylic acid octafluoro pentyl ester, vinylformic acid 19 fluorine esters, the vinylformic acid perfluoro capryl ethyl ester.
3. a kind of emulsion for low-surface energy coating according to claim 1 is characterized in that alkyl methacrylate is a kind of or several arbitrarily in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, Isooctyl methacrylate, 2-Ethylhexyl Methacrylate, lauryl methacrylate(LMA), stearyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester, the methacrylic acid hydroxy butyl ester.
4. a kind of emulsion for low-surface energy coating according to claim 1 is characterized in that alkyl acrylate is a kind of or several arbitrarily in methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, Octyl acrylate or Isooctyl acrylate monomer, 2-EHA, lauryl acrylate, octadecyl acrylate, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, the vinylformic acid hydroxy butyl ester.
5. a kind of emulsion for low-surface energy coating according to claim 1 is characterized in that the pH value buffer reagent is any one in yellow soda ash, sodium bicarbonate, sodium phosphate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, bicarbonate of ammonia, the ammoniacal liquor.
6. a kind of emulsion for low-surface energy coating according to claim 1 is characterized in that emulsifying agent is any several composition that contains in the reactive emulsifier of unsaturated double-bond.
7. a kind of emulsion for low-surface energy coating according to claim 1 is characterized in that initiator is a kind of in Potassium Persulphate, the ammonium persulphate.
8. the preparation method of an emulsion for low-surface energy coating as claimed in claim 1 is characterized in that step is:
The 1st step joined water, initiator, emulsifying agent, pH value buffer reagent in the reactor in proportion, was warming up to 60～80 ℃,
In the 2nd step, the mixed solution to reactor dropping alkyl methacrylate, alkyl acrylate, hydroxyalkyl acrylamide, fluorinated acrylate, the large monomer of fluorine silicon reacts in proportion, lower the temperature behind reaction times 4～12h,
The 3rd step, survey pH value, pH value is 7.0～9.0 to get final product.
A kind of emulsion for low-surface energy coating according to claim 8 the preparation method, it is characterized in that adding an amount of pH value conditioning agent in the reactor, regulate pH value to 7.0～9.0.
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| CN104513340B (en) * | 2015-02-06 | 2016-08-17 | 中国船舶重工集团公司第七二五研究所 | A kind of fluorine silica acrylic acid is from polishing antifouling resin and preparation method thereof |
| CN108715720A (en) * | 2018-06-19 | 2018-10-30 | 界首市黑马渔具有限公司 | A kind of preparation method of resistant silica gel bionic fish bait |
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| CN101348595A (en) * | 2008-07-28 | 2009-01-21 | 北京大学 | Fluorine-silicon modified self-crosslinking acrylic ester emulsion and preparation thereof |
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